Process of treating oils



Aug. 2, 1932. w. SHIFFLER ET AL PROCESS OF TREATING 011.5

Filed June 5, 1929 Feds fl'on C harrrbe r amp flea?" Excharyer Patented Aug. 2, 1932 UNITED STATES PATENT OFFICE WILLIAM H. SHIFFLER, MELVIN M. HOLE, AND MARVIN F. MILLER, BERKELEY,

CALIFORNIA, ASSIGNOBS TO STANDARD O11 COMPANY OF CALIFORNIA, OF SAN FRANCISCO, CALIFORNIA, A CORPORATION OF DELAWARE rnocnss or rename OILS Application filed June a, 1929. Serial No. 867,889.

This invention relates to a process of treating petroleum distillates for use as motor fuel. The process of this invention is particularly adapted to the treatment of oils obtained from the conversion of higher boiling point oils by the use of metallic halides.

Various types of oils distillates and particularly gasoline, kerosene and other fractions obtained by the conversion of high boilw ing point oils into lower boiling point oils by treatment with a metallic halide, contain hydrochloric acid and chlorine. Fractions of the character stated have long been considbined form which is incapable of removal by said ordinary treatment.

The removal of substantially all of the chlorine, whether it occurs in the form of hydrochloric acid or in some other form is important, for the reason that an oil fraction containing chlorine or chlorine compounds, when used as a fuel in internal combustion engines will corrode the metal parts thereof, particularly in the presence of moisture.

An object of this invention is to disclose and provide a process of decomposing and removing fixed chlorides present in oils produced from heavier oils by the use of metallic halides.

Another object is to disclose and provide a process of rendering motor fuels non-corroprovide a method of dechlorinating oils by the use of heat and catalytic materials.

In order to facilitate the description ofthe process as embodied in one modification thereof, reference will be had to the appended drawing which diagrammatically illustrates one arrangement of apparatus adapted to carry out the process.

As has been stated before, oils contain'chlorine in the form of hydrochloric acid, and also additional chlorine which is not removable by water washing. This latter chlorine exists in some form of combination as organic chlorides. The present process is particularly adapted to the removal of such compounds.

The actual amount of chlorine present in the fixed form (which may be determined by analyses after the hydrochloric acid has been removed), is very small, usually less than 0.1 percent. Gasolines produced from heavler oils by an aluminum chloride conversion, for example, have fixed chloride'contents of from 0.01 to 0.1 percent. I

It has been discovered that fixed chlorides present in oils may be materially reduced or changed in character so that they may be removed by a subsequent water wash, by subjecting the oils to the action of heat. Temperatures of over 300 F. and preferably temeratures above 400 F. should be employed.

y subjecting these .oils to temperatures of above 300 or 400 F. the fixed chlorides are apparently decomposed and hydrochloric the oil being treated to the action of heat while in contact with a catalytic solid material of extended surface area, even though said catalytic solid material is chemically inert. For example, when the oil is subjected to a temperature of 300 F. or higher, and then passed through or maintained in contact with a solid material of extended surface while at such temperature, a material increase in the quantity of fixed chloride which has been decomposed or rendered removable by subsequent washing may be obtained.

Catalytic materials capable of facilitating the process without themselves undergoing any chemical change are such materials as pumice, bauxite, pure aluminum oxide, coke, quartz, glass, inert silicates and chlorides of iron, zinc, nickel, cobalt, barium, copper and the like. All of these substances apparently bring about and facilitate a decomposition of the organic chlorides present in the oil so as to form hydrogen chloride or hydrochloric acid, which in turn may be readily removed from the oil by a subsequent treatment.

The process may also be carried out by sub ect1ng the oils to a temperature above 300 F., in the presence of substances which act both as catalysts and as chemical reagents. For example, an oil may be subjected to temperatures of over 300 F. in the presence of materials such as ferrous sulphide. lime, zinc, iron, copper, aluminum, etc. These materials apparently react with the-fixed organic chlorides present in the oil,

changing into chlorides during the reaction and in this manner reducing the chloride content of the oil.

Materials such as themetals zinc, iron, copper, aluminum, etc., apparently exert a chemical effect upon the oil at the beginning of the process and reduce the chlorine content of the oil by combining chemically with the chlorides present in the oil.

After the reaction has taken place, further reduction in chloride content of the oils appears to take place in a purely catalytic manner, that is, the iron, zinc or copper chlorides which have been formed during the first part of. the process do not react chemically with the o l. but act catalytically upon the fixed chlorides present therein so as to decompose said chlorides. I The final result is the same, whether the reaction proceeds catalytically or by chemical reaction. The effect of heat as such 1S ,th0f (p1urse,ca1 ctonstant accompaniment of e1 er e ca a ic or the chemi dechlorination. y cal type of In carrying out the process the distillate 0r condensate which it is desired to treat, such as condensate from an aluminum chloride still, is run to a storage tank from which it ts picked up by a pump and circulated through a heater in which the distillate is heated'to a temperature preferably over 300 F. Temperatures of from 300 to- 900 F. have been very successfully used, the pressure during such treatment ranging from atmospheric to 200 or even 400 pounds per square inch, depending on the nature of the distillate and whether it is desired to treat the distillate 1n the liquid or vapor phase.

The vapor phase process may be successfully carried out'at atmospheric pressure, but it is usually more convenient to carry out the process in the liquid phase. The heated distillate may then be discharged from -the heater into the bottom of a vertical tower packed with one of the materials, catalysts or reagents mentioned hereinabove. For example, the heated distillate may be discharged into the bottom of a vertical tower packed with ferrous sulphide which can conveniently be in lump form. The distillate may then he recirculated through the tower and the heater until contact between the distillate and the reagent or catalytic material has been maintained for a'suiiicient length of time. It has been found that the amount of chlorine removed or rendered removable depends upon the contact time and temperature, a greater reduction in chloride content being obtained with longer periods of contact and higher temperature. The 'heater and the tower or reaction chamber is'preferably held under such pressure as is necessary to maintain the oil in a liquid state.

After the oil has been in contact with the treating materials at a treating temperature for a predetermined period of time, say onehalf hour or one hour, it may be pumped into a tower counter-flow to a spray of water. The distillate or oil obtained from the top of the water tower is cool, free from hydrochloric acid, and in all respects a finished product much more suitable for use than products obtained heretofore. The color of the oil during such treatment is usuall not changed, but if necessary the treated distillate may be rcdistilled or otherwise treated.

It is to be understood that it is not necessary to always include the steps of washing the oil with an alkaline solution and /or with water after carrying out the process of this invention. The use of caustic and water washing is entirely a matter of acidity of the treated distillate, although it is preferable to at least water wash the oil and remove the hydrochloric acid formed during the process.

A process of the hereinabove character may, of course, be carried out in any suitable 4 type of apparatus, the apparatus shown on the attached drawing being merely illustrative of an arrangement of units which may be employed.

As shown in the appended drawing, the petroleum distillate or crude gasoline from a condenser or from a suitable storage tank may be supplied by a line 10 to a pump 11. and then passed through a line 12 into a heat exchanger 13. The distillate from the heat exchanger may then pass by means of line 14; into a heater 15, from which it may be discharged through line 16 into a reaction or catalytic chamber 17. The reaction chamber 17 may be suitably insulated. as by the covering 18, or it may be steamjacketed, or other means of maintaining the chamber 17 at a. desired temperature be provided.

I tion chamber 17 by line 19 may pass through the heat exchanger 13 so as to impart some of the heat'contained therein to the incoming distillate. The cooled, treated distillate may then be discharged by line 20, provided with a suitable pressure release valve 21, into a washing and settling chamber 22. A valved line 23 provided with a suitable spray head near the upper portion of the settling chamber 22, may supply water which would be dissemenated through the upwardly flowing treated oil, and collect in the lower portion of the washing and settling apparatus 22, from which it may be withdrawn by the valved outlet 24. The treated and washed distillate may then be discharged through a suitable outlet 25 to storage.

Although a particular process and method of carrying out the same has been described in detail hereinabove, it will be understood that the invention is not to be limited to the specific process so described, but includes all modifications and changes which come within the scope of the appended claims.

We claim; 1. In a process of dechlorinating distillates of gasoline and kerosene types, the step of subjecting a condensate having an initial boiling point of below 300 F'obtained from a metallic halide conversion of heavy boiling point mineral oil, said condensate containing a fractional quantity of chlorine other than hydrogen chloride, to a temperature of over about three hundred degrees F. for a period of time sufiicient to decompose such combined chlorine.- a

2. In a process of dechlorinating mineral oils having an initial boiling point of below 300 F, the step of subjecting a motor fuel distillate, having an initial boiling point of below 300 F. and containing combined chlorine which is not removable by washing with water to a temperature of over about three hundred degrees F. for a period of time sufficient to decompose such combined chlorine,

and under a .superatmospheric pressure adapted to maintain said-oil in a liquid state, and then removing the chlorine compounds resulting fromsuch treatment whereby a mineral oil suitable for use as a motor fuel stock is produced.

liquid state whereby a mineral oil suitable for use as a motor fuel stock is produced.

4. A 7 process of dechlorinating mineral oils, comprising the steps of subjecting a condensate from a metallic halide conversion of heavy boiling point oil, said condensate having an initial boiling point of'below 300 F. and containing a fractional quantity of combined chlorine which is not removable by washing with water, to a temperature of over about three hundred degrees F. for a period of time suificientto decompose such chlorine compounds, and under a superatmospheric pressure adapted to maintain said condensate in a liquid state, and then removing the chlorine compounds resulting from such treatment.

5.'In a process of dechlorinating gasoline distillates, the step ofsubjecting a gasoline type condensate from a metallic halide conversion of heavy boiling point mineral oils, said condensate containing a fractional quantity of organic chlorine compounds, to a temperature of over about three hundred degrees F. in the presence of a solid catalytic agent adapted to decompose such combined chlorine.

' 6. In aprooess of dechlorinating gasoline distillates, the steps of subjecting a gasoline type condensate from a metallichalide conversion of heavy boiling point mineral oil, said condensate containing a fractional quantity of organic chlorine compounds, to a temperature of over about three hundred degrees F. in the presence of a solid catalytic agent, under a superatmospheric pressure adapted to maintain said oil in a liquid state, and for a time sulficient to decompose such combined chlorine.

7. A process of dechlorinating}; gasoline distillates, including the steps of subjecting a gasoline type condensate from a metallic halide conversion of heavy boiling point mineral oil, said condensate containing a fractional quantity ofcombined chlorine which is not removable by washing with water, to a tem perature of over about three hundred degrees F. in the presence of a solid catalytic agent, and under a superatmospheric pressure adapted to maintain said oil in a liquid state, for a period of time sulficient to decompose said combined chlorine, and then removing the chlorine compounds resulting from such treatment from the oil.

8. In a process of dechlorinating distillates having an initial boiling point of below 300 an initial boiling point of below 300 F.', containing about 0.1% of combined chlorine which is not removable'by washing with stantially solid reagent capable of combining with said combined chlorine whereby a min- F., the step of subjecting a distillate having eral oil suitable for use as a motor fuel stock is produced.

9. In a process of dechlorinating mineral oils, the step of subjecting a distillate having an initial boiling point of 300 F., containing about 0.1% of combined chlorine which is not removable by washing with water, to a temperature of over about three hundred degrees F., in the presence of a substantially solid reagent capable of combining with said combined chlorine, and under a superatmospheric ressure adapted to maintain said oil in a iquid state whereby a mineral oil suitable for use as a motor fuel stock is produced.

10. In a process of dechlorinating gasoline distillates, the step of subjecting a gasoline type condensate from a metallic halide conversion ofheavy boiling point mineral, said condensate containing less than about 0.1% of chlorine other than hydrogen chloride, to a temperature of over about three hundred degrees F. in the presence of a substantially solid reagent capable of combining with said combined chlorine whereby a gasoline distillate suitable for use as a motor fuel stock is produced.

11. In a process of dechlorinating distillates having an initial boiling point of below 300 F., the step of contacting a condensate from a metallic halide conversion of heavy boiling point mineral, said condensate having an initial boiling point of below 300 F. and containing less than about 0.1% of chlorine other than hydrogen chloride, at a temperature of over about three hundred degrees F. and under a superatmospheric pressure adapted to maintain said oil in a liquid state, with a substantially solid reagent capable of combining with said combined chlorine whereby a mineral oil suitable for use as a motor fuel stock is produced.

12. In a process of dechlorinating distillates having an initial boiling point of below 300 F., the step of contacting a motor fuel distillate, having an initial boiling point of below 300 F. and containing a fractional quantity of chlorine other than hydrogen chlorine, with a solid material capable of combining with said chlorine compounds so as to form materials capable of effecting a decomposition of said chlorine compounds, at a temperature of over about three hundred degrees F., whereby a mineral oil suitable for use as a motor fuel stock is produced.

13. In a process of dechlorinating gasoline type'distillates, the step of contacting a gasoline type distillate, containing less than about 0.1% of chlorine which is not removable by washing with water,with solid materials capable of combining with said chlorine, so as to form materials capable of effecting a decomposition of further quantities of said chlorine, at a temperature of over about three hundred. degrees F., and at a superatmospheric pressure. adapted to maintain said oil in a liquid state.

14. A process of dechlorinating gasoline type distillates, comprising the steps of contacting gasoline type distillate from a metallic halide conversion of heavy boiling point mineral oils, said condensate containing a fractional quantity of chlorine which is not removable by washing with water, with solid materials capable of combining with said chlorine, so as to form materials capable of effecting a decomposition of further quantities of said chlorine, at a temperature of over about three hundred degrees F.

15. A process of dechlorinating distillates having an initial boiling point of below 300 F., comprising the steps of contacting a condensate froma metallic halide conversion of heavy boiling point mineral oil, said condensate having an initial boiling point of below 300 F. and containing a fractional quantity of organic chlorine compounds, with solid materials capable of combining with said organic chlorine to form materials capable of effecting a decomposition of further quantities of said organic chlorine compounds, at a temperature of over about three hundred degrees F.. and under a superatmospheric pressure adapted to maintain said oils in a liquid state.

16. A process of dechlorinating distillates having an initial boiling point of below 300 F., comprising the steps of contacting a condensate from a metallic halide conversion of heavy boiling point mineral oil, said condensate having an initial boiling point of below 300 F. and containing less than about 0.1% of organic chlorine compounds, with solid materials capable of combining withsaid organic chlorine to form materials capable of effecting a decomposition of further quantities of said organic chlorine compounds, at a temperature of over about three hundred degrees F.. and under a superatmospheric pressure adapted to maintain said oils in a liquid state, and then removing the chlorine compounds resulting from such treatment, from the treated oil.

17 In a process of dechlorinating hydrocarbon distillates whereby non-corrosive distillates suitable for use as a motor fuel are chlorine compounds, to a temperature of over about 300 F. in the presence of a substantially solid' reagent capable of combining with said combined chlorine.

r 1 19. Ina process of dechlorinating hydro agout 300 F. in the presence of ferrous sule. lggsgned at Richmond, this 21st day of May, 15

' WILLIAM H. SHIFFLER.

MELVIN M. HOLM. MARVIN F. MILLER.

' carbon distillates whereby non-corrosive d18- tillates suitablefor use as motor fuel are produced, the ste of subjecting a distillate having an initial Boiling point below 300 F. and

10 containing a fractional quantity of or anic chlorine compounds, to a temperature 0 over 

